Glass transition in 1,4-polybutadiene: Mode-coupling theory analysis of molecular dynamics simulations using a chemically realistic model

Abstract

We present molecular dynamics simulations of the glass transition in a chemically realistic model of 1,4-polybutadiene (PBD). Around 40 K above the calorimetric glass transition of this polymer the simulations reveal a well-developed two-stage relaxation of all correlation functions. We have analyzed the time-scale separation between vibrational degrees of freedom (subpicosecond dynamics) and the alpha relaxation behavior (nanosecond to microsecond dynamics) using the predictions of mode-coupling theory (MCT). Our value for the mode-coupling critical temperature Tc agrees perfectly with prior experimental estimates for PBD. The predictions of MCT for the scaling behavior of the so-called beta relaxation, the plateau regime separating vibrational dynamics and the alpha relaxation, are well fulfilled. Furthermore, we are able to derive a consistent set of MCT exponents, completely characterizing the scaling behavior of relaxation processes in the vicinity of Tc. For the temperature dependence of the alpha relaxation we find deviations from MCT predictions which we trace to the influence of torsional barriers on the atomic motions.